Abstract

AbstractLower‐order streams (first‐ and second‐order) define the initial, landscape‐related, chemical signature of stream water in catchments. To date, first‐order streams have been perceived as predominantly draining systems, which collect water and solutes from the surrounding groundwater and surface runoff and simply mirror the chemical composition of the inputs. In this study, the impact of stream‐groundwater exchange fluxes on water chemistry of a first order agricultural stream (Schönbrunnen) and its connected groundwater in south‐western Germany was assessed combining222Rn, dissolved ions (chloride, sulphate, nitrate), and salt tracer tests with investigations of stream discharge and groundwater hydraulic gradients. The findings suggest that stream‐water chemistry in lower‐order streams is governed by an intricate interplay between dynamic, bidirectional water and solute exchange between groundwater and the stream leading to a pronounced hydrologic turnover along the studied reaches. High nitrate concentrations (up to 79 mg/L as NO3−) in stream water were attenuated in downstream direction (a mean value of 39 mg/L) without an increase in discharge, suggesting that redox processes occurring during sediment passage in sequential infiltration and exfiltration zones affect stream water chemistry. Nitrate in stream water infiltrating into the aquifer at distinct losing spots was subject to denitrification within the first few decimetres of the streambed, while concurrent exfiltration of low‐nitrate groundwater into the stream at gaining spots compensated for flow losses and in turn diluted instream nitrate concentrations. In summary the findings imply that (1) instream mixing resulting from the bidirectional exchange of water between groundwater and the stream (hydrologic turnover) affects instream nitrate concentrations, (2) denitrification in the streambed of losing reaches and the near‐stream aquifer significantly contributes to reactive nitrate turnover and elimination, and (3) oxidation of ammonium could be a secondary source of nitrate inputs into the stream.

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